Effect of pore chemistry regulations on CO2 capture efficiency: Charge transfer between anchored first-row transition open metal sites and frameworks

MFU-Sc exhibits the highest CO2 adsorption capacity of 15.57 mmol/g at 298 K and 1.0 bar among MFU-Ms (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn). The correlation coefficient between CO2 capture capacity and charge transfer of OMS-framework is 0.976. This reveals the impact of pore chemistry regulations on CO2 capture capacities via charge transfer of OMS-framework. [Display omitted] •CO2 adsorption capacity reaches 15.57 mmol g−1 in MFU-Sc with a selectivity of 145.7/302.74 for CO2 over CH4/N2 at 298 K and 1.0 bar.•Pore space polarity modification increased CO2 capture capacity, selectivity, isothermal adsorption heat and Coulomb interactions.•Charge transfer of OMS-framework and CO2 capture capacity exhibit a coefficient of 0.976.•Pore chemistry regulations enhance CO2 capture capacities via charge transfer of OMS-framework. Deteriorating atmospheric environmental issues have spurred the innovation of carbon capture and storage (CCS) technologies to mitigate the greenhouse effect. Developing high-performance adsorbents is a prerequisite in CCS processes. Herein, a series of metal–organic frameworks (MOFs), MFU-M (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn), were constructed by anchoring first row transition metals as open metal sites (OMSs) in MFU-4 l-Li. Density function theory (DFT) and grand canonical Monte Carlo (GCMC) simulations were employed to explore the effect of pore chemistry regulations on CO2 adsorption performance in MFU-Ms. Results highlight that MFU-Sc displayed outstanding CO2 adsorption capacity of 15.57 mmol/g, followed by MFU-Ti (14.21 mmol/g) and MFU-V (10.70 mmol/g) at 298 K and 1.0 bar. Isothermal adsorption heat, van der Waals/Coulomb interactions, and gas distribution are analyzed to illustrate the effects of pore chemistry regulation. A high degree of similarity is observed in the variation of Coulomb interaction and CO2 capture capacity. Furthermore, a high correlation coefficient of 0.976 was identified between CO2 capture capacity and charge transfer of OMS-framework, underscoring the pivotal role of charge transfer of OMS-framework in pore chemistry regulations.